JP2009057515A - Gelling agent, gel-like composition, and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gel-like composition having characteristic visco-elasticity and having high stability and safety even at a temperature area of nearly room temperature. <P>SOLUTION: The gelling agent or the gel-like composition comprises a sucrose fatty acid ester having a HLB value of 11-18, a surfactant having a HLB value of 3 to less than 11, an ionic surfactant having a Krafft point of 25°C or less, and/or a nonionic surfactant having a sterol group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a gelling agent and a gel composition, and a cleaning agent, a cosmetic, and a pharmaceutical using the same.

  In the fields of detergents, cosmetics, pharmaceuticals, and the like, various polymers, inorganic compounds, surfactants, and the like are used as gelling agents in order to improve handling properties and maintain dosage forms. For example, natural polymers such as polysaccharides and casein as polymers, synthetic polymers such as polyoxyethylene and acrylic acid polymers, and inorganic compounds include various clay minerals such as montmorillonite and silica, Furthermore, anionic, cationic, amphoteric, and nonionic surfactants are appropriately selected and used as the surfactant according to the purpose and effect of the gelling agent.

  Patent Documents 1 to 3 show gelling agents containing sucrose fatty acid diesters.

  On the other hand, it is a viscoelastic fluid that exhibits high viscosity by forming long string-like micelles called Worm-like micelles by entangled with surfactant molecules. There is a system called (Non-Patent Document 1). Viscoelastic fluids have both great viscosity and great elasticity, and many studies have been made on aqueous solutions of quaternary ammonium salt surfactants in the presence of tightly bound counterions, such as cetylpyridinium salicylate. (Non-Patent Document 2). Further, hexadecyltrimethylammonium bromide, which is another cationic surfactant, also exhibits viscoelastic behavior in the presence of a large amount of salt (Non-patent Document 3).

Patent Document 4 discloses hair and skin using a viscoelastic surfactant aqueous solution containing an anionic surfactant as an essential component and containing an amphoteric surfactant, a nonionic surfactant, an electrolyte, and a water-soluble polymer. A cleaning agent is shown. Among them, preferred viscoelastic behavior is described in the use of the body cleansing agent, and viscoelastic behavior in taking out from the container and application on the skin is discussed. If the elasticity is too large, coating becomes difficult, which is not preferable. On the other hand, if the viscosity is too high, the liquid remaining from the outlet of the container will be drawn forever. Appropriate solution behavior is obtained only when elasticity and viscosity are balanced. The preferred flow behavior and application behavior are that the shear elastic modulus G ₀ of the viscoelastic fluid is 50 Pa to 500 pa, and the frequency range in which the dynamic storage elastic modulus G ′ and the dynamic loss elastic modulus G ″ coincide with each other is 0.00. are to be obtained when it is 1 rad · s ^-1 or more 60rad · s ^-1 or less.
Furthermore, in Patent Document 5, a sucrose fatty acid ester or / and a polyglycerin fatty acid ester having a specific range of HLB value and a surfactant having a specific range of HLB value are used in combination, and viscoelastic behavior with excellent usability is exhibited. A thickening gelling agent is described.

JP-A-5-279651 JP-A-7-26244 JP 7-26245 A US596550 JP 2005-82650 A Current Opinion in Colloid & Interface Science 6 (2001) 451-456 H. Hoffmann and H.M. Rehage, in Surfactant Solutions, Surfactant Science Series, vol. 22, R.M. Zana, Ed. , New York, 1987, p. 209 A. Khatory et al, Langumuir, vol. 9, p. 1456 (1993)

  When using gelling agents in pharmaceuticals and cosmetics, these are required to have high safety in order to be used on the human body. Is required, that is, good usability. Also, when used as a body cleaning agent such as shampoo or body soap, it is preferable that safety is high, and a product having excellent usability is required. For this reason, the gelling agent used for the above purpose is required to have both high safety, preferable usability, and good thickening gelling ability. Nothing was known enough to satisfy the point.

For example, polymer-based materials are relatively safe and exhibit good thickening gelation ability when added in small amounts. Has a feeling of use. Clay minerals have high thixotropic properties and are refreshing to use and are preferable in terms of usability, but are liable to be separated and unstable. A variety of surfactants are used, but there are problems with safety, they are easily affected by the liquid composition such as salt concentration and pH, and the elongation at the time of application is insufficient. Therefore, the feeling of use when applied on the skin was not sufficient.
Further, viscoelastic fluids are not sufficiently suitable for pharmaceutical and cosmetic applications from the viewpoint of safety.
Since the thickening gel composition obtained in Patent Document 5 has a high crystal precipitation temperature in the composition, its viscoelasticity will be lost over time if its excellent viscoelasticity is stored in a temperature range of about room temperature (30 ° C or lower). Stable viscoelasticity was not obtained.
As described above, the gel-like composition having the viscoelastic behavior described above has been desired to be developed for use in pharmaceuticals and cosmetics because it has a stable usability even in a temperature range of about room temperature.

As described above, when the gelling agent and the gel-like composition are used for body washing agents, cosmetics, pharmaceuticals, etc., high safety, preferable usability in a temperature range of about room temperature, and good thickening gelling ability. However, in the prior art, it was not possible to obtain a sufficient gelling agent having all of them. In particular, it has been a problem to stably exhibit viscoelastic behavior in a temperature range of about room temperature. Further, the inventors of the present invention particularly have a G ₀ of 100 Pa or more and a dynamic storage elastic modulus G
Range of frequencies' match 'dynamic loss modulus G and' is around 0.01, when more information is 0.001 rad · s ^-1 or 1 rad · s ^-1 or less, a characteristic viscoelastic It has been found that the gel composition shown can be obtained.

As a result of intensive studies to solve the above problems, the present inventors have found that a sucrose fatty acid ester having a specific range of HLB values, a surfactant having a specific range of HLB values, and an ionicity having a specific range of Kraft points. By using a surfactant and / or a nonionic surfactant having a specific skeleton in combination, the present inventors have found a gelling agent having a gelling ability exhibiting the above excellent viscoelastic behavior.
That is, the first gist of the present invention is that (a) a sucrose fatty acid ester having an HLB value of 11 or more and 18 or less, (b) a surfactant having an HLB value of 3 or more and less than 11, and (c-1) a Kraft point of 25 ° C. or less. The ionic surfactant and / or (C-2) a gelling agent containing a nonionic surfactant having a sterol skeleton.

And the 2nd-3rd summary of this invention exists in following (2)-(7).
(2) The gelling agent wherein the monoester content of the sucrose fatty acid ester of the gelling agent (3) (a), wherein (b) is a nonionic surfactant, is 50 to 100%.
(4) A gel composition containing the gelling agent.
(5) A cleaning agent comprising the gel composition.
(6) A cosmetic comprising the gel composition.
(7) A pharmaceutical product containing the gel composition.

Further, the preferable flow behavior and application behavior are that the shear elastic modulus G ₀ of the viscoelastic fluid is 50 Pa to 500 pa, and the frequency range in which the dynamic storage elastic modulus G ′ and the dynamic loss elastic modulus G ″ coincide with each other is Although it is said that it is obtained when it is 0.1 rad · s ⁻¹ or more and 60 rad · s ⁻¹ or less, the inventors particularly note that G ₀ is 100 Pa or more and the dynamic storage elastic modulus G ′ dynamic range of frequencies the loss modulus G '' is matched, near 0.01, more information when it is 0.001 rad · s ^-1 or 1 rad · s ^-1 or less, a gel exhibiting characteristic viscoelastic It has been found that a composition can be obtained.

  By using the gelling agent according to the present invention, it is possible to obtain a gel-like composition having characteristic viscoelasticity and having high stability and safety even in a temperature range of about room temperature.

Hereinafter, the present invention will be described in detail.
[Gelling agent]
A gelling agent is an agent that thickens and gels the aqueous medium to which it is added. The gelling agent of the present invention is an ionic surfactant having a Kraft point of 25 ° C. or lower, which is a hydrophobic surfactant (c-1) component which is a sucrose fatty acid ester (b) component which is the following component (a), and / Or (C-2) A nonionic surfactant having a sterol skeleton as a component is contained.
In the present invention, the HLB values of the polyethylene glycol type and polyhydric alcohol type nonionic surfactants are defined by the following Griffin equation (1).
HLB value = (molecular weight of hydrophilic group / molecular weight of surfactant) × 20 (1)
In the case of an ionic surfactant, the HLB value is different from the HLB value obtained by the above formula and the actual behavior. A phase diagram in a system mixed with a surfactant or oil is prepared, and calculated using the HLB composition calculated at that time.

<(A) component: sucrose fatty acid ester>
The sucrose fatty acid ester used in the present invention has an HLB value of 11 or more and 18 or less, and preferably 11 or more and 16 or less. If the HLB value is too low, the solubility in water may decrease and precipitation may occur. If the HLB value is too high, the ability to form corded micelles may decrease and thickening gelation may not occur.
The constituent fatty acid of the sucrose fatty acid ester may be a saturated fatty acid or an unsaturated fatty acid, may be a linear fatty acid or a branched fatty acid, and may further have a substituent such as a hydroxyl group. The carbon number of the constituent fatty acid is usually 6 or more, preferably 10 or more, more preferably 12 or more, and usually 22 or less, preferably 18 or less, more preferably 16 or less. If the number of carbon atoms of the constituent fatty acid is too small, the ability to form corded micelles may be reduced, and thickening gelation may not occur. If it is too much, the melting point of the hydrated crystals in the composition will be high, and stability at low temperatures will occur. May decrease. Two or more of these fatty acids may be used in combination.
Specifically, as these fatty acids, for example, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, partoleic acid, stearic acid, isostearic acid, Examples include oleic acid, linoleic acid, behenic acid, erucic acid, ricinoleic acid, and hydroxystearic acid.
The monoester content of the sucrose fatty acid ester is usually 50 to 100%, preferably 70 to 100%, and more preferably 90 to 100%. If the monoester content is low and there are many components above the diester, lamellar liquid crystals are easier to form than string micelles, and thickening gelation may not occur or favorable viscoelastic behavior even if thickening gelation occurs Cannot be obtained.

<(B) Component: Surfactant>
The surfactant which is the component (b) used in the present invention has an HLB value of usually 3 or more, preferably 5 or more, and usually 11 or less, preferably 9 or less. If the HLB value is too low, the solubility in water may decrease and precipitate, and if the HLB value is too high, the ability to form corded micelles may decrease and thickening gelation may not occur.
As long as the surfactant of component (b) is within the above HLB value, any kind of anionic, cationic, amphoteric, and nonionic is usable, but a nonionic surfactant is preferred. Anionic surfactants include fatty acid soaps, ether carboxylic acids and their salts, alkane sulfonates, higher fatty acid ester sulfonates, dialkyl sulfosuccinates, higher fatty acid amide sulfonates, alkyl allyl sulfonates, Higher alcohol sulfate, secondary higher alcohol sulfate, alkyl and alkyl allyl ether sulfate, glycerol fatty acid ester sulfate, higher fatty acid alkylolamide sulfate ester, sulfated oil, alkyl phosphate ester salt Etc. Cationic surfactants include alkylamine salts, polyamine or alkanolamine fatty acid derivatives, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, dialkylmorpholiniums. Examples of amphoteric surfactants include salts such as alkylamino fatty acid salts, alkylbetaines, and alkylamine oxides. Nonionic surfactants include sucrose fatty acid ester, polyglycerin fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl Examples include ethers, polyoxyethylene fatty acid esters, fatty acid alkanolamides, polypropylene glycol polyethylene glycol condensates, polyoxyethylene hydrogenated castor oil, and sucrose fatty acid esters, polyglycerin fatty acid esters, glycerin fatty acid esters, propylene glycol fatty acid esters. , Sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester Le is preferable. These surfactants may be used alone or in combination of two or more.

<(C-1) component: ionic surfactant having a Kraft point of 25 ° C. or lower>
The ionic surfactant which is the component (c-1) used in the present invention has a Kraft point of 25 ° C. or lower, preferably 20 ° C. or lower. The Kraft point of an ionic surfactant is defined as the temperature at which its solubility increases rapidly and represents the solubility of the surfactant in water. If the Kraft point is too high, a hydrated solid of the surfactant may precipitate in the solution in a temperature range of about room temperature, and gelation may not occur. As long as the ionic surfactant of component (c-1) is within the above Kraft point, any kind of anionic, cationic, and amphoteric can be used, but a preferable ionic surfactant is an anionic surfactant. Examples of the agent include alkyl sulfates such as sodium dodecyl sulfate, polyoxyethylene alkyl ether sulfates such as dodecyl polyoxyethylene sulfate, and fatty acid soaps such as sodium laurate. Examples of the cationic surfactant include alkyltrimethylammonium salts such as dodecyltrimethylammonium bromide, and examples of the amphoteric surfactant include alkylamino fatty acid salts, alkylbetaines, and alkylamine oxides.

<(C-2) component: nonionic surfactant having a sterol skeleton>
The nonionic surfactant having a sterol skeleton as the component (c-2) used in the present invention has a cholesteryl group or a phytosteryl group in a hydrophobic group, preferably a nonionic surfactant having a cholesteryl group It is an agent. By having a sterol skeleton in the hydrophobic group, the ability to form string micelles is improved and gelation is likely to occur. The nonionic surfactant having a cholesteryl group is polyoxyethylene cholesteryl ether, and the nonionic surfactant having a phytosteryl group is polyoxyethylene phytosteryl ether, and polyoxyethylene cholesteryl ether is particularly preferable.
The HLB value of the component (c-2) is not particularly affected as long as the above conditions are satisfied.
The HLB value is 11 or more and 18 or less, and particularly preferably 11 or more and 16 or less. If the HLB value is too low, the melting point of the hydrated crystals in the composition becomes high and stability at low temperatures cannot be obtained. If the HLB value is too high, the ability to form corded micelles decreases and thickening gelation occurs. There may not be.
The gelling agent of the present invention usually comprises (a) component, (b) component and (c-1) component and / or (c-2) component, but the range in which the effects of the present invention are not impaired. And may contain other components. Moreover, you may use together the nonionic surfactant which has the sterol frame | skeleton which is (c-2) component and the ionic surfactant with a Kraft point of 25 degrees C or less which is (c-1) component.

<Mixing ratio of gelling agent>
When the component (c-1) and / or the component (c-2) is the component (c), the component (a), (
The mixing ratio of the component (b) and the component (c) is such that the component (b) / ((a) component + (b) component + (c) component) is weight%, usually 0.01% or more, preferably 0 .1% or more, more preferably 1% or more, usually 70% or less, preferably 50% or less, and more preferably 30% or less. In addition, (a) component / ((a) component + (c) component) is usually 30% by weight.
Thus, it is preferably 50% or more, more preferably 60% or more, usually 99.99% or less, preferably 99.9% or less, more preferably 99% or less.

<Method for preparing gelling agent>
The gelling agent of the present invention does not necessarily need to be homogenized. However, it is easier to prepare a gel-like composition and the preparation time can be shortened. The homogenization of the gelling agent can be performed by stirring and mixing the components. When the viscosity is too high at room temperature and mixing is difficult, stirring and mixing may be performed in a state where the fluidity is increased by heating. In addition, when mixing the powdery component and the liquid component, first dissolve the powdery component in an appropriate solvent such as water or alcohol, and then add the liquid component thereto and mix with stirring. Then, the solvent may be distilled off for preparation.

[Gel composition]
The gel composition of the present invention is a thickened or gelled composition, and contains an aqueous component as a gelling agent and component (d). A preferable mixing ratio of the gelling agent and the aqueous component is that the gelling agent / (gelling agent + aqueous component) is in weight%, usually 0.01% or more, preferably 0.1% or more, more preferably 1%. These are usually 70% or less, preferably 50% or less, and more preferably 30% or less.

<(D) component: aqueous component>
The aqueous component of the present invention usually means water, but may be a mixed solution of water and alcohol such as ethanol, ethylene glycol, glycerin, propylene glycol or the like. In the case of a mixed solution of water and alcohol, the mixing ratio is not particularly limited, but the water content is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight in the solvent. That's it.

<Other ingredients>
The gel composition of the present invention may contain other components depending on its use. For example, when used for a cleaning agent, a chelating agent may be blended in order to sufficiently exert the cleaning power. By using this chelating agent, not only can the white turbidity of the hard water aqueous solution due to the generation of scale in hard water containing calcium, magnesium, etc. be prevented, but also the detergency, foaming power, and foam feel in hard water can be maintained. it can. Such a chelating agent is not particularly limited, and those used in the past are used, and specifically, citrate, malate, tartrate, glutamate, pyrophosphate, polyacrylate, polymaleic acid Salt, gluconate, nitrilotriacetic acid salt, acrylic acid-maleic anhydride copolymer salt, maleic anhydride-methyl vinyl ether copolymer salt, maleic anhydride-olefin copolymer salt, maleic anhydride-methacrylic acid copolymer Examples of the salt of coalescence, maleic anhydride-tartaric acid condensate, zeolite, tripolyphosphate, ethylenediaminetetraacetic acid (EDTA), ethylenediamine and the like. Among these, citrate, malate, tartrate, glutamate, pyrophosphate, etc. are highly safe to the human body, have no environmental pollution, and water, alcohol, etc. constituting the gel composition It is preferably used because of its high compatibility and excellent cleaning power, dirt dispersibility, foaming power, and foam feel. One or more chelating agents selected from these groups are usually contained in the gel composition of the present invention in an amount of 0.01 to 50% by weight, preferably 1 to 30% by weight.

  In addition to the above, the gel composition of the present invention may be added by selecting any of the additive components commonly used in ordinary detergent compositions within a range that does not impair the purpose of the present invention. May be. Examples of such additional components include organic acid monoglycerides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, fatty acid alkanolamides, Or a carboxybetaine type, an imidazolinium type, a sulfobetaine type, a surfactant that is mild to the human body such as an amino acid surfactant, an inorganic builder such as sodium carbonate, sodium sulfate, sodium chloride, magnesium sulfate, calcium chloride, Fluidity improvers such as glycerin, ethanol, propylene glycol, polyethylene glycol, thickeners such as carboxymethylcellulose, hydroxyethylcellulose, and more Fee, colorants, humectants, disinfectants, enzymes, and the like anti-inflammatory agents.

<Method for preparing gel composition>
The gel composition of the present invention can be obtained by uniformly dissolving a gelling agent and, if necessary, other components in an aqueous component.

[Detergents, cosmetics, and pharmaceuticals containing a gel composition]
The gel composition of the present invention can be used for various products exhibiting a gel at normal temperature as a cleaning agent, cosmetics, medicine, food, deodorant, bath agent, fragrance, deodorant and the like. Above all, it is suitable for use in detergents, cosmetics and pharmaceuticals. Examples of the cleaning agent include food cleaning agents, dish cleaning agents, kitchen cleaning agents, facial cleansers, body soaps, shampoos, rinses and the like. Cosmetics include creams, emulsions, lotions, cleansing agents, bath cosmetics, moisturizing cosmetics, blood circulation promoting / massaging agents, pack cosmetics, hair cosmetics, and the like. Examples of pharmaceuticals include ointments, molded cataplasms, sustained-release preparation bases, drug delivery system carriers, gels for electrophoresis, and the like. Gel-like compositions are mainly used as pharmaceutical bases.

[Dynamic viscoelastic behavior of gel composition]
The gel composition obtained in the present invention preferably exhibits a Maxwell fluid behavior. In the Maxwell fluid, the following equation holds in the dynamic viscoelasticity.
G ′ = G ₀ ω ² τ ² / (1 + ω ² τ ² )
G ″ = G ₀ ωτ / (1 + ω ² τ ² )
| Η * | = (G ′ + G ″) ^1/2 / ω
Here, ω (rad · s ⁻¹ ) is a frequency, τ (s) is a relaxation time, G ₀ (Pa) is a shear elastic modulus, G ′ (Pa) is a dynamic storage elastic modulus, G ″ (Pa). Is the dynamic loss modulus, | η * | (Pa
S) is the complex viscosity. In general, the complex viscosity may be considered as the viscosity at the shear rate ω.

In this equation, ωτ> 1 on the high frequency side, that is, the region where the shear rate is high, and G ′ and G ₀ are substantially equal. When G ′ = G ″, G ₀ = 2G ′ and τ = 1 / ω.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to an Example. In addition, unless otherwise specified, the blending amount is indicated by weight%.

(Examples 1-7, Comparative Examples 1-24)
[Preparation of gel composition]
A gel composition was prepared using a surfactant having the composition shown in Table 1 as a gelling agent. The gel composition was prepared by adding (d) component to (a) component, (b) component, and (c) component, and stirring and mixing.

[Thickening gelation state]
Using an AR-G2 from TA Instruments, the viscosity at a shear rate of 0 was measured as a static viscosity at 25 ° C. Moreover, based on this, the state of thickening gelation was evaluated in five stages of A to E as follows.
The melting point of the hydrated crystals in the composition of Table 1 was determined by observing the dissolved state at the temperature of the composition and measuring the temperature at which the hydrated crystals melt.
In general, polyethylene glycol-type nonionic surfactants are so low that no Kraft point is observed, and therefore, “less than 0 ° C.” is described as a reference value.

Thickness of 100 Pa · s or more Viscoelastic gel A
10 Pa · s or more and less than 100 Pa · s Gel B
0.1 Pa · s or more and less than 10 Pa · s Thickening C
0.1 Pa · s or less Thickening gelation is insufficient D
Not valuable Composition separated E

[Measurement of dynamic viscoelasticity]
For Examples 1 to 3 and 5, in order to measure dynamic viscoelasticity, Rheometric Scientific FE Ltd's ARES1KFRTN1-FCO was used, and complex viscosity | η * |, dynamic storage elastic modulus G ′, dynamic The loss elastic modulus G ″ was measured. The results are shown in FIGS.

[Good elongation]
As can be seen from FIGS. 1 to 4, in Examples 1 to 3 and 5, as the shear rate ω increases, | η *
The viscosity represented by | decreases. That is, it is perceived that the viscosity of the gel is reduced by the shear applied when applied onto the skin, and the elongation is good.

[Dynamic viscoelastic properties]
In Examples 1 to 3 and 5, the shear elastic modulus G ₀ is 100 Pa or more, and from FIGS.
Dynamic storage modulus G 'and the dynamic loss modulus G' range of frequencies 'match (omega _{G' = G '')} is 0.001 rad · s ^-1 or 1 rad · s ^-1 or less. That is, Examples 1-3, 5 show that it is a gel composition showing good and characteristic dynamic viscoelasticity.

FIG. 3 is a diagram showing the dynamic viscoelasticity of Example 1. It is the figure which measured the dynamic viscoelasticity of Example 2. FIG. It is the figure which measured the dynamic viscoelasticity of Example 3. FIG. It is the figure which measured the dynamic viscoelasticity of Example 5. FIG.

Claims (7)

(A) sucrose fatty acid ester having an HLB value of 11 or more and 18 or less, (b) a surfactant having an HLB value of 3 or more and less than 11, and (c-1) an ionic surfactant having a Kraft point of 25 ° C. or less and / or (C -2) A gelling agent containing a nonionic surfactant having a sterol skeleton.   The gelling agent according to claim 1, wherein (b) is a nonionic surfactant.   The gelling agent according to claim 1 or 2, wherein the sucrose fatty acid ester (a) has a monoester content of 50 to 100%.   The gel-like composition containing the gelatinizer in any one of Claims 1-3.   A cleaning agent comprising the gel composition according to claim 4.   A cosmetic comprising the gel composition according to claim 4.   A pharmaceutical comprising the gel composition according to claim 4.